반응 #1806541

반응 방정식

(2S,4S)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine

N-methylmorpholine

diphenylphosphinyl chloride

→

(2S,4S)-4-(diphenylphosphino)-2-[(diphenylphosphino)methyl]-1-(diphenylphosphinyl)-pyrrolidine

수율 76.8%

용매

toluene

toluene

반응 조건

후처리

1. 1
   기타which was provided with a stirrer
2. 2
   workup.ADDITIONwas then added dropwise
3. 3
   여과The mixture was then filtered through a sintered glass suction
4. 4
   여과filter
5. 5
   기타the filtrate was evaporated on a rotary evaporator at 60° C./17 mbar
6. 6
   workup.ADDITIONtreated with 30 ml of 3N hydrochloric acid
7. 7
   기타The ether phase was then separated
8. 8
   추출the aqueous phase was extracted a further twice with 30 ml of diethyl ether each time
9. 9
   건조The extracts were dried over sodium sulphate
10. 10
    여과filtered off
11. 11
    농축concentrated on a rotary evaporator at 60° C./17 mbar
12. 12
    기타For purification the residue (1.57 g)
13. 13
    기타was chromatographed over 140 g of Kieselgel 60 (0.063 to 0.20 mm granular size)
14. 14
    workup.ADDITIONA mixture of benzene/ethyl acetate/ethanol (8:2:1)
15. 15
    기타After evaporation of the solvent
16. 16
    기타drying for 16 hours/1 mbar

실험 절차

1.01 g (2.23 mmol) of (2S,4S)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine, 1.46 ml (13.38 mmol) of N-methylmorpholine and 30 ml of toluene were placed in a 500 ml sulphonation flask which was provided with a stirrer, thermometer, dropping funnel and argon gasification. While stirring there was then added dropwise thereto at room temperature within 10 minutes a solution of 0.79 g (3.35 mmol) of diphenylphosphinyl chloride in 10 ml of toluene. The reaction was finished after 7 hours. The mixture was then filtered through a sintered glass suction filter and the filtrate was evaporated on a rotary evaporator at 60° C./17 mbar. The residue (2.2 g) was taken up in 30 ml of diethyl ether and treated with 30 ml of 3N hydrochloric acid. The ether phase was then separated and the aqueous phase was extracted a further twice with 30 ml of diethyl ether each time. The extracts were dried over sodium sulphate, filtered off and concentrated on a rotary evaporator at 60° C./17 mbar. For purification the residue (1.57 g) was chromatographed over 140 g of Kieselgel 60 (0.063 to 0.20 mm granular size). A mixture of benzene/ethyl acetate/ethanol (8:2:1) was used as the eluant. After evaporation of the solvent and drying for 16 hours/1 mbar, there was obtained 1.12 g (76.8%) of pure (2S,4S)-4-(diphenylphosphino)-2-[(diphenylphosphino)methyl]-1-(diphenylphosphinyl)-pyrrolidine. Melting point: sintering from 65° C., clear melting at 130° C. [α]D20 =-21.4° (c=0.5 in benzene).

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